Detergent compositions containing an anionic surfactant and a 4,4&#39;-bis(triazinylamino)-stilbene disulphonic acid optical brightener

ABSTRACT

An aqueous, isotropic liquid detergent composition comprising an aqueous solution of: 
     a) an anionic surfactant; and 
     b) an optical brightener of formula I ##STR1## in which X is hydrogen, NH 4 .sup.⊕, or a cation of an alkali metal, an alkaline earth metal or an organic amine; 
     R 1  is selected from morpholino or anilino unsubstituted or substituted by 1, 2 or 3 groups selected from C 1-4  alkyl, C 1-4  alkoxy and halogen; piperidinyl, unsubstituted or substituted by 1 or 2 C 1-4  alkyl groups; hexamethyleneimino, pyrrolidino, C 1-8  alkylamino; C 1-8  dialkylamino; or a 2,2,6,6-tetramethylpiperidinyl residue; 
     R 2  has a significance of R 1  independently of R 1  ; 
     provided that when both groups R 1  (or R 2 ) are morpholino or unsubstituted anilino, the other groups R 2  (or R 1  respectively), are not both unsubstituted anilino.

The invention relates to stilbene derivatives for use in detergent compositions.

According to the invention, there is provided an aqueous, isotropic, liquid detergent composition comprising an aqueous solution of

(a) an anionic surfactant; and

(b) an optical brightener of formula I ##STR2## in which X is hydrogen, NH₄ ⁺, or a cation of an alkali metal, an alkaline earth metal or an organic amine;

R₁ is selected from morpholino or anilino unsubstituted or substituted by 1, 2 or 3 groups selected from C₁₋₄ alkyl, C₁₋₄ alkoxy and halogen; piperidinyl, unsubstituted or substituted by 1 or 2 C₁₋₄ alkyl groups; hexamethyleneimino, pyrrolidino, C₁₋₈ alkylamino; di(C₁₋₈ alkyl)amino; or a 2,2,6,6-tetramethylpiperidinyl residue;

R₂ has a significance of R₁ independently of R₁ ;

provided that when both groups R₁ (or R₂) are morpholino or unsubstituted anilino, the other groups R₂ (or R₁ respectively), are not both unsubstituted anilino.

Preferably a composition according to the invention is phosphate-free.

Preferably 2 to 60%, more preferably 5 to 40%, of anionic surfactant is present in a composition according to the invention.

Preferably 0.05 to 1.5%, more preferably 0.1 to 1%, of optical brightener is present in a composition according to the invention.

Preferably a composition according to the invention may also contain builders. Preferred builders are those described in British Patent Application No. 2,187,749A (the content and preferences of which are incorporated herein by reference).

Preferably a composition according to the invention contains an enzyme. Preferably when enzyme is present in a composition according to the invention, it is present in an amount of 0.05-2% by weight. Preferred enzymes are proteases, amylases, lipases, glucose-oxidases, cellulases, more preferably Marcatase enzyme and Termarnyl enzyme.

Preferably a composition according to the invention contains a sequestrant for metal ions (which may be present in water used in a washing process in which a composition according to the invention is used). Preferably when sequestrant, is present, it is present in an amount of 0.1 to 3% by weight, more preferably 0.4 to 1.2%. Preferred sequestrants are alkylene polyamino-polyalkylene polycarboxylic acids and/or polyphosphonic acids, especially diethylene triamine pentaacetic acid; triethylene tetraamine hexaacetic acid and tetraethylene pentamine heptaacetic acid.

Preferably a composition according to the invention contains a performance booster. The preferred amount of performance booster when present is 0.5 to 5% of composition. Preferred performance boosters include ethoxylated amines, more preferably tetraethylene pentamine, preferably ethoxylated with 15 to 19 moles of ethylene oxide.

Preferred anionic surfactants are C₂₋₄ alkoxysulphates of C₈₋₂₂ alcohols; C₉₋₂₂ alkyl benzene sulphonic acids and salts thereof; R₂₀ -SO₃ -M, where R₂₀ is a C₁₂₋₂₂ alkyl group and M is hydrogen or an alkali metal cation, C₁₀₋₁₈ alkyl sulphates containing 0 to 4 ethyleneoxide units per mole of alkyl sulphate; water soluble salts of C₈₋₂₄ alkyl sulphonates; C₈₋₁₈ alcohol ether sulphonates; C₈₋₁₂ alkyl phenol-(C₂ H₅ --O--)₁ to 4 ether sulphates; C₁₀₋₂₀ alkyl (C₂ H₅ --O--)₁ to 4 ether sulphates; water soluble salts of C₁₋₁₀ esters of alpha-sulphonates of C₆₋₂₂ fatty acids; water soluble salts of 2-C₂₋₉ acyloxy-C₉₋₂₃ alkane-1-sulphonic acids; water soluble salts of C₁₂₋₁₄ alkenyl sulphonates and beta-C₁₋₃ alkoxyC₈₋₂₀ alkane sulphonates.

Preferably a composition according to the invention contains a non-ionic surfactant. Preferably the amount of non-ionic surfactant when present is 5-20% by weight, provided the total amount of surfactant in the composition is not more than 60%. Preferred non-ionic surfactants are described in British Patent Application No. 2,187,749.

Preferably a composition according to the invention may include a cationic surface active agent. Among cationic surfactants are for example, quaternary ammonium, amine or amine oxide surfactants. Preferred cationic surface active agents are those described in British Patent Application No. 2,187,749. Preferably the amount of cationic surfactant, when present is 5 to 20%, provided the total amount of surfactant is not more than 60%.

The contents and preferences of British Patent Application No. 2,187,749 are incorporated herein by reference.

Compositions according to the invention can also contain other surfactants known in the art such as non-ionic, cationic, zwitterionic and ampholytic surfactants. Preferably the total amount of surfactant is from 15% to 60% inclusive, more preferably from 20 to 45% inclusive. Suitable examples of these optional surfactants are described in U.S. Pat. Nos. 4,285,841 and 3,929,678.

Compositions according to the invention may also contain other additives such as a C₁₀₋₂₂ alkyl or alkenyl fatty acid, the carboxy groups of which may be ethoxylated by 1 to 10 ethylene oxide units. Such additives are preferably present in an amount of from 3 to 30% by weight of the composition.

Preferred fatty acids are selected from coconut fatty acid and oleic acid, more preferably topped whole cut coconut fatty acid and oleic acid.

Preferably when an acid is present in a composition according to the invention, a base to neutralise the acid is also present. Preferably such a base is an ethanolamine, for example N-methylethanolamine.

Preferred 2,2,6,6-tetramethylpiperidine residues include ##STR3## where R₄ is --OH or --NH₂ or esters or amides thereof or ##STR4##

Preferably both SO₃ X groups are in 2-position with respect to the ethene (--CH═CH--) group.

Preferably both groups R₁ are the same.

Preferably at least one of the groups R₁ is piperidinyl, unsubstituted or substituted by 1 or 2 C₁₋₄ alkyl groups.

Preferably R₁ is R₁ ' where R₁ ' is anilino, unsubstituted or monosubstituted by C₁₋₄ alkyl; piperidinyl, unsubstituted or substituted by 1 or 2 C₁₋₄ alkyl groups; hexamethyleneimino; pyrrolidino, propylamino or dipropylamino. More preferably R₁ is R₁ " where R₁ " is piperidinyl unsubstituted or mono- or di-substituted by C₁₋₄ alkyl (preferably CH₃).

Preferably R₂ is R₂ ' where R₂ " is anilino, unsubstituted or substituted by one or two groups selected from halogen (preferably Cl), C₁₋₄ alkyl (preferably CH₃) and C₁₋₄ alkoxy (preferably OCH₃).

In this Specification any halogen is fluoro, chloro, bromo or iodo, preferably chloro or bromo, more preferably chloro.

Preferably any C₁₋₄ alkyl group is methyl or ethyl, more preferably methyl.

Preferably any C₁₋₄ alkoxy is methoxy or ethoxy, more preferably ethoxy.

Preferably X is X' where X' is hydrogen, Na⊕, K⊕ or NH₄ ⊕.

Most preferably each R₁ is R₁ "' where R₁ "' is piperidinyl, unsubstituted or substituted by 1 or 2 methyl groups and each R₂ is R₂ " where R₂ " anilino unsubstituted or mono-substituted by methyl.

Preferably any piperidinyl group as R₁ or R₂ is attached to the triazinyl group through the heterocyclic N-atom.

Compounds of formula I are known and may be made from known compounds by known methods.

Preferably the composition according to the invention is a liquid laundry detergent composition.

Compositions according to the invention may also include enzyme stabilising agents, polyacids, soil removal agents, antiredeposition agents, sud regulants, hydrotropes, opacifiers, antioxidants, bactericides, dyes, perfumes and other brighteners known in the art. Such components are generally present in total as no more than 15%, preferably 2 to 12%.

One of the disadvantages of liquid detergent compositions containing stilbene optical brighteners is their inability to produce both excellent build-up and good resistance to brightener staining. Brighteners deposit onto fabrics where they absorb U.V. radiant energy and re-emit it as a blue light. This reduces or eliminates any yellowish cast to fabrics and gives them a bright appearance. However, undesirable brightener staining can occur when liquid detergents come into direct contact with cotton-containing fabrics, such as during pre-treatment. The present invention reduces or eliminates such staining while maintaining an acceptable level of fabric brightening. This good balance of properties is surprising. For example detergent compositions containing a compound of formula I where R₁ is unsubstituted anilino and R₂ is 4-sulpho anilino (as the optical brightener) show poor resistance to brightener staining whilst having a good build up. On the other hand for example detergent compositions containing compounds of formula I where R₁ is methoxy and R₂ is --O--C₆ H₅ show good resistance to brightener staining but have a very poor build up.

Advantages of the detergent compositions according to the invention include good build up and good resistance to brightener staining.

In this Specification, where a symbol appears more than once in a formula, its significances are independent of one another unless indicated to the contrary.

All percentages given in this Specification are by weight of the composition unless indicated otherwise.

EXAMPLE 1

The compound of formula 1a ##STR5## in sodium salt form; is added to the following composition: 7.2% of C₁₃ linear alkylbenzene sulphonic acid

10.8% of C₁₄₋₁₅ alkyl polyethoxylate (2.25) sulphuric acid

6.5% of C₁₂₋₁₃ alcohol polyethoxylate (6.5)*

1.2% of C₁₂ alkyl trimethylammonium chloride

13.0% of C₁₂₋₁₄ fatty acid

2.0% of oleic acid

4.0% of citric acid (anhydrous)

0.23% of diethylenetriamine pentaacetic acid

1.5% of TEPA-E₁₅₋₁₈ **

2.0% of monoethanolamine

1.66% of sodium ion

2.65% of potassium ion

7.25% of propylene glycol

7.75% of ethanol

0.66% of formic acid

0.13% of the compound of formula 1a

Balance to 100% of minors and water.

EXAMPLE 2

A composition is formulated comprising:

    ______________________________________                                         C.sub.11-18 linear alkyl benzene sulphonic acid                                                              11%                                              C.sub.14-15 alcohol polyethoxylate 7 EO                                                                      12%                                              Topped whole cut coconut fatty acid                                            Chain length mixture;                                                          C.sub.10 (5%), C.sub.12 (55%), C.sub.14 (22%), C.sub.18                                                      20.5%                                            Oleic acid (10%)                                                               C.sub.10-11 isoparaffins      4%                                               Diethyl phthalate             6%                                               Cyclohexylamine               2%                                               Monomethyl ethanolamine       4.3%                                             Potassium citrate monohydrate 2.4%                                             (63.5% in water)                                                               Dequest 2060 S                1.7%                                             Tetraethylene pentamine ethoxylated with                                                                     1.5%                                             15-18 moles of ethylene oxide                                                  Ethanol                       3%                                               Potassium hydroxide (50% in water)                                                                           3%                                               Formic acid                   0.2%                                             CaCl.sub.2 2H.sub.2 O         0.05%                                            The compound of formula 1a    0.18%                                            Marcatase enzyme              0.71%                                            Termarnyl 300L enzyme         0.10%                                            Water, perfume etc.           Balance                                          ______________________________________                                    

The compositions of Examples 1 or 2 can be directly used as liquid detergents in an aqueous laundry bath at 100 ml/10 liters.

EXAMPLE 3

A composition is formulated comprising:

    ______________________________________                                         C.sub.12 linear alkylbenzene sulphonic acid                                                             10.2%                                                 Triethanolamine coconut alkyl sulphate                                                                  3.9%                                                  C.sub.13-15 alcohol polyethoxylate (7 EO)                                                               11.7%                                                 Topped whole cut coconut fatty acid                                                                     10.7%                                                 Oleic acid               3.9%                                                  Citric acid (anhydrous)  0.9%                                                  Diethylenetriamine pentamethylene-                                                                      0.85%                                                 phosphoric acid                                                                Triethanolamine          4.4%                                                  Sodium hydroxide         3.0%                                                  Propylene glycol         2.8%                                                  Ethanol                  5.8%                                                  Sodium formate           1.0%                                                  Brightener of formula 1a (of Example 1)                                                                 0.18%                                                 Minors + Water           Balance to                                                                     100%                                                  ______________________________________                                    

This composition can be used directly as a liquid detergent in an aqueous laundry bath at 100 ml/10 liters.

EXAMPLES 4 and 5

Example 1, 2 or 3 is repeated using instead of the compound of formula 1a an appropriate amount of one of the following compounds:

The compound of formula 4a ##STR6##

The compound of formula 5a ##STR7##

EXAMPLES 6 to 19

Compounds of the formula ##STR8## where R₁ and R₂ are defined in the Table below, can be added to a composition according to Example 1, 2 or 3.

                  TABLE                                                            ______________________________________                                         EX. No.                                                                               R.sub.1         R.sub.2                                                 ______________________________________                                          6                                                                                     ##STR9##                                                                                       ##STR10##                                               7                                                                                     ##STR11##                                                                                      ##STR12##                                               8                                                                                     ##STR13##                                                                                      ##STR14##                                               9                                                                                     ##STR15##                                                                                      ##STR16##                                              10                                                                                     ##STR17##                                                                                      ##STR18##                                              11                                                                                     ##STR19##                                                                                      ##STR20##                                              12                                                                                     ##STR21##                                                                                      ##STR22##                                              13                                                                                     ##STR23##                                                                                      ##STR24##                                              14                                                                                     ##STR25##                                                                                      ##STR26##                                              15                                                                                     ##STR27##                                                                                      ##STR28##                                              16                                                                                     ##STR29##      NHCH.sub.2 CH.sub.2 CH.sub.3                            17                                                                                     ##STR30##                                                                                      ##STR31##                                              18     NHCH.sub.3                                                                                      ##STR32##                                              19     NHC.sub.2                                                                                       ##STR33##                                              ______________________________________                                     

What is claimed is:
 1. An aqueous, isotropic liquid detergent composition comprising an aqueous solution of(a) an anionic surfactant and (b) and optical brightener of formula I ##STR34## in which X is hydrogen, NH₄ ⁺, or a cation of an alkali metal, an alkaline earth metal or an organic amine and R₁ and R₂, independently, are selected from morpholino and anilino unsubstituted or substituted by 1, 2 or 3 groups selected from C₁₋₄ alkyl, C₁₋₄ alkoxy and halogen; piperidinyl, unsubstituted or substituted by 1 or 2 C₁₋₄ alkyl groups; hexamethyleneimino; pyrrolidino; C₁₋₈ alkylamino; C₁₋₈ dialkylamino; and a 2,2,6,6-tetramethylpiperidinyl residue; provided that at least one R₁ is unsubstituted piperidinyl.
 2. A detergent composition according to claim 1, in which, in the compound of formula I, R₁ is R₁ ' is anilino, unsubstituted or monosubstituted by C₁₋₄ alkyl; piperidinyl, unsubstituted or substituted by 1 or 2 C₁₋₄ alkyl groups; hexamethyleneimino; pyrrolidino; propylamino or dipropylamino.
 3. A detergent composition according to claim 1,in which, in the compound of formula I, both groups R₁ are piperidinyl, unsubstituted or substituted by 1 or 2 methyl and the groups R₂ are either both unsubstituted anilino or both o-toluidinyl.
 4. A detergent composition according to claim 1, containing one or more of the following:(a) an enzyme (b) a sequestrant for metal ions; (c) an ethoxylated amine as a performance booster; (d) a non-ionic, cationic, zwitterionic or ampholytic surfactant; (e) a builder; (f) a fatty acid.
 5. An aqueous detergent composition according to claim 1, containing one or more of the following:(a) 2 to 60% by weight of anionic surfactant (b) 0.05 to 1.5% by weight of the compound of formula I; (c) 0.05 to 2% by weight of enzyme; (d) 0.1 to 3% by weight of sequestrant; (e) 0.5 to 2% by weight of ethoxylated tetraethylene pentamine as a performance booster; (f) 0.5 to 20% by weight of non-ionic, cationic, zwitterionic or ampholytic surfactants; (g) 0.5 to 2% builders; (h) 5 to 20% fatty acid, and (i) the balance being waterprovided the total amount of surfactant is no more than 60%.
 6. A composition according to claim 1 wherein both groups R₁ are the same.
 7. A composition according to claim 1 wherein R₂ is R₂ ' where R₂ ' is anilino, unsubstituted or substituted by 1 or 2 groups selected from C₁₋₄ alkyl, halogen and C₁₋₄ alkoxy.
 8. A composition according to claim 6 wherein R₂ is R₂ ' where R₂ ' is anilino, unsubstituted or substituted by 1 or 2 groups selected from C₁₋₄ alkyl, halogen and C₁₋₄ alkoxy.
 9. A composition according to claim 3 containing 2 to 60%, by weight, of anionic surfactant and 0.05 to 1.5%, by weight, of compound of formula I.
 10. A composition according to claim 1 containing 2 to 60%, by weight, of anionic surfactant and 0.05 to 1.5%, by weight, of compound of formula I.
 11. A composition according to claim 6 containing 2 to 60%, by weight, of anionic surfactant and 0.05 to 1.5%, by weight, of compound of formula I.
 12. A composition according to claim 7 containing 2 to 60%, by weight, of anionic surfactant and 0.05 to 1.5%, by weight, of compound of formula I.
 13. A composition according to claim 8 containing 2 to 60%, by weight, of anionic surfactant and 0.05 to 1.5%, by weight, of compound of formula I.
 14. A composition according to claim 3 wherein the anionic surfactant is selected from the group consisting of C₂₋₄ alkoxysulphates of C₈₋₂₂ alcohols; C₉₋₂₂ alkyl benzene sulphonic acids and salts thereof; R₂₀ -SO₃ -M, where R₂₀ is a C₁₂₋₂₂ alkyl group and M is hydrogen or an alkali metal cation; C₁₀₋₁₈ alkyl sulphates containing 0 to 4 ethyleneoxide units per mole of alkyl sulphate; water soluble salts of C₈₋₂₄ alkyl sulphonates; C₈₋₁₈ alcohol ether sulphonates; C₈₋₁₂ alkyl phenol-(C₂ H₅ --O--)₁₋₄ ether sulphates; C₁₀₋₂₀ alkyl (C₂ H₅ --O--)₁₋₄ ether sulphates; water soluble salts of C₁₋₁₀ esters of alpha-sulphonates of C₆₋₂₂ fatty acids; water soluble salts of 2-C₂₋₉ acyloxy-C₉₋₂₃ alkane-1-sulphonic acids; water soluble salts of C₁₂₋₁₄ alkenyl sulphonates and beta-C₁₋₃ alkoxyC₈₋₂₀ alkane sulphonates.
 15. A composition according to claim 1 wherein the anionic surfactant is selected from the group consisting of C₂₋₄ alkoxysulphates of C₈₋₂₂ alcohols; C₉₋₂₂ alkyl benzene sulphonic acids and salts thereof; R₂₀ -SO₃ -M, where R₂₀ is a C₁₂₋₂₂ alkyl group and M is hydrogen or an alkali metal cation; C₁₀₋₁₈ alkyl sulphates containing 0 to 4 ethyleneoxide units per mole of alkyl sulphate; water soluble salts of C₈₋₂₄ alkyl sulphonates; C₈₋₁₈ alcohol ether sulphonates; C₈₋₁₂ alkyl phenol-(C₂ H₅ --O--)₁₋₄ ether sulphates; C₁₀₋₂₀ alkyl (C₂ H₅ --O--)₁₋₄ ether sulphates; water soluble salts of C₁₋₁₀ esters of alpha-sulphonates of C₆₋₂₂ fatty acids; water soluble salts of 2-C₂₋₉ acyloxy-C₉₋₂₃ alkane-1-sulphonic acids; water soluble salts of C₁₂₋₁₄ alkenyl sulphonates and beta-C₁₋₃ alkoxyC₈₋₂₀ alkane sulphonates.
 16. A composition according to claim 6 wherein the anionic surfactant is selected from the group consisting of C₂₋₄ alkoxysulphates of C₈₋₂₂ alcohols; C₉₋₂₂ alkyl benzene sulphonic acids and salts thereof; R₂₀ -SO₃ -M, where R₂₀ is a C₁₂₋₂₂ alkyl group and M is hydrogen or an alkali metal cation; C₁₀₋₁₈ alkyl sulphates containing 0 to 4 ethyleneoxide units per mole of alkyl sulphate; water soluble salts of C₈₋₂₄ alkyl sulphonates; C₈₋₁₈ alcohol ether sulphonates; C₈₋₁₂ alkyl phenol-(C₂ H₅ --O--)₁₋₄ ether sulphates; C₁₀₋₂₀ alkyl (C₂ H₅ --O--)₁₋₄ ether sulphates; water soluble salts of C₁₋₁₀ esters of alpha-sulphonates of C₆₋₂₂ fatty acids; water soluble salts of 2-C₂₋₉ acyloxy-C₉₋₂₃ alkane-1-sulphonic acids; water soluble salts of C₁₂₋₁₄ alkenyl sulphonates and beta-C₁₋₃ alkoxyC₈₋₂₀ alkane sulphonates.
 17. A composition according to claim 7 wherein the anionic surfactant is selected from the group consisting of C₂₋₄ alkoxysulphates of C₈₋₂₂ alcohols; C₉₋₂₂ alkyl benzene sulphonic acids and salts thereof; R₂₀ -SO₃ -M, where R₂₀ is a C₁₂₋₂₂ alkyl group and M is hydrogen or an alkali metal cation; C₁₀₋₁₈ alkyl sulphates containing 0 to 4 ethyleneoxide units per mole of alkyl sulphate; water soluble salts of C₈₋₂₄ alkyl sulphonates; C₈₋₁₈ alcohol ether sulphonates; C₈₋₁₂ alkyl phenol-(C₂ H₅ --O--)₁₋₄ ether sulphates; C₁₀₋₂₀ alkyl (C₂ H₅ --O--)₁₋₄ ether sulphates; water soluble salts of C₁₋₁₀ esters of alpha-sulphonates of C₆₋₂₂ fatty acids; water soluble salts of 2-C₂₋₉ acyloxy-C₉₋₂₃ alkane-1-sulphonic acids; water soluble salts of C₁₂₋₁₄ alkenyl sulphonates and beta-C₁₋₃ alkoxyC₈₋₂₀ alkane sulphonates.
 18. A composition according to claim 8 wherein the anionic surfactant is selected from the group consisting of C₂₋₄ alkoxysulphates of C₈₋₂₂ alcohols; C₉₋₂₂ alkyl benzene sulphonic acids and salts thereof; R₂₀ -SO₃ -M, where R₂₀ is a C₁₂₋₂₂ alkyl group and M is hydrogen or an alkali metal cation; C₁₀₋₁₈ alkyl sulphates containing 0 to 4 ethyleneoxide units per mole of alkyl sulphate; water soluble salts of C₈₋₂₄ alkyl sulphonates; C₈₋₁₈ alcohol ether sulphonates; C₈₋₁₂ alkyl phenol-(C₂ H₅ --O--)₁₋₄ ether sulphates; C₁₀₋₂₀ alkyl (C₂ H₅ --O--)₁₋₄ ether sulphates; water soluble salts of C₁₋₁₀ esters of alpha-sulphonates of C₆₋₂₂ fatty acids; water soluble salts of 2-C₂₋₉ acyloxy-C₉₋₂₃ alkane-1-sulphonic acids; water soluble salts of C₁₂₋₁₄ alkenyl sulphonates and beta-C₁₋₃ alkoxyC₈₋₂₀ alkane sulphonates.
 19. A composition according to claim 9 wherein the anionic surfactant is selected from the group consisting of C₂₋₄ alkoxysulphates of C₈₋₂₂ alcohols; C₉₋₂₂ alkyl benzene sulphonic acids and salts thereof; R₂₀ -SO₃ -M, where R₂₀ is a C₁₂₋₂₂ alkyl group and M is hydrogen or an alkali metal cation; C₁₀₋₁₈ alkyl sulphates containing 0 to 4 ethyleneoxide units per mole of alkyl sulphate; water soluble salts of C₈₋₂₄ alkyl sulphonates; C₈₋₁₈ alcohol ether sulphonates; C₈₋₁₂ alkyl phenol-(C₂ H₅ --O--)₁₋₄ ether sulphates; C₁₀₋₂₀ alkyl (C₂ H₅ --O--)₁₋₄ ether sulphates; water soluble salts of C₁₋₁₀ esters of alpha-sulphonates of C₆₋₂₂ fatty acids; water soluble salts of 2-C₂₋₉ acyloxy-C₉₋₂₃ alkane-1-sulphonic acids; water soluble salts of C₁₂₋₁₄ alkenyl sulphonates and beta-C₁₋₃ alkoxyC₈₋₂₀ alkane sulphonates.
 20. A composition according to claim 11 wherein the anionic surfactant is selected from the group consisting of C₂₋₄ alkoxysulphates of C₈₋₂₂ alcohols; C₉₋₂₂ alkyl benzene sulphonic acids and salts thereof; R₂₀ -SO₃ -M, where R₂₀ is a C₁₂₋₂₂ alkyl group and M is hydrogen or an alkali metal cation; C₁₀₋₁₈ alkyl sulphates containing 0 to 4 ethyleneoxide units per mole of alkyl sulphate; water soluble salts of C₈₋₂₄ alkyl sulphonates; C₈₋₁₈ alcohol ether sulphonates; C₈₋₁₂ alkyl phenol-(C₂ H₅ --O--)₁₋₄ ether sulphates; C₁₀₋₂₀ alkyl (C₂ H₅ --O--)₁₋₄ ether sulphates; water soluble salts of C₁₋₁₀ esters of alpha-sulphonates of C₆₋₂₂ fatty acids; water soluble salts of 2-C₂₋₉ acyloxy-C₉₋₂₃ alkane-1-sulphonic acids; water soluble salts of C₁₂₋₁₄ alkenyl sulphonates and beta-C₁₋₃ alkoxyC₈₋₂₀ alkane sulphonates.
 21. A composition according to claim 13 wherein the anionic surfactant is selected from the group consisting of C₂₋₄ alkoxysulphates of C₈₋₂₂ alcohols; C₉₋₂₂ alkyl benzene sulphonic acids and salts thereof; R₂₀ -SO₃ -M, where R₂₀ is a C₁₂₋₂₂ alkyl group and M is hydrogen or an alkali metal cation; C₁₀₋₁₈ alkyl sulphates containing 0 to 4 ethyleneoxide units per mole of alkyl sulphate; water soluble salts of C₈₋₂₄ alkyl sulphonates; C₈₋₁₈ alcohol ether sulphonates; C₈₋₁₂ alkyl phenol-(C₂ H₅ --O--)₁₋₄ ether sulphates; C₁₀₋₂₀ alkyl (C₂ H₅ --O--)₁₋₄ ether sulphates; water soluble salts of C₁₋₁₀ esters of alpha-sulphonates of C₆₋₂₂ fatty acids; water soluble salts of 2-C₂₋₉ acyloxy-C₉₋₂₃ alkane-1-sulphonic acids; water soluble salts of C₁₂₋₁₄ alkenyl sulphonates and beta-C₁₋₃ alkoxyC₈₋₂₀ alkane sulphonates.
 22. A composition according to claim 1 wherein, in the compound of formula I, both groups SO₃ X are in the 2-position with respect to the --CH═CH-- group.
 23. A composition according to claim 1 wherein any piperidinyl group as R₁ or R₂ is attached to the triazine group through the heterocyclic N-atom.
 24. A composition according to claim 22 wherein any piperidinyl group as R₁ or R₂ is attached to the triazine group through the heterocyclic N-atom.
 25. A composition according to claim 21 wherein, in the compound of formula I, both groups SO₃ X are in the 2-position with respect to the --CH═CH-- groups and any piperidinyl group as R₁ is attached to the triazine group through the heterocyclic N-atom.
 26. A composition according to claim 8 wherein the compound of formula I is a compound of the formula ##STR35## wherein both groups R₁ are of the formula ##STR36## and both groups R₂ are the same as R₁ or are unsubstituted anilino or 2-methylanilino.
 27. A composition according to claim 26 wherein both groups R₂ are unsubstituted anilino. 